Chemical Combination for the Generation of Disinfectant and Heat

ABSTRACT

This invention comprises a lightweight, portable chemical combination of reagents for sterilizing or disinfecting objects in the absence of electrical power or fire. The chemical combination includes a chemical oxidant with the capacity to liberate a biocidal intermediate, a chemical reductant of the oxidant with the capacity to react with the oxidant, and an effector to induce a reaction between the oxidant and reductant. In one embodiment, the oxidant comprises chlorite, the reductant comprises sulfite, and the effector comprises ascorbate. In another embodiment, the chemical combination comprises the oxidant, reductant, effector and iron-activated magnesium. When water or water solutions are added to either embodiment, the chemical combination generates heat, steam and a biocidal intermediate that can destroy contaminating microorganisms. In one embodiment, the biocidal intermediate is a halogen-based biocidal intermediate, such as chlorine dioxide. In another embodiment, the biocidal intermediate is a halogen-free biocidal intermediate.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.10/988,442, filed Nov. 10, 2004, entitled “Chemical Combination for theGeneration of Disinfectant and Heat”, now U.S. Pat. No. ______.

STATEMENT OF GOVERNMENT INTEREST

The invention described herein may be manufactured and used by the U.S.Government for Governmental purposes without the payment of any royaltythereon.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention generally relates to a safe, portable chemicalcombination of reagents which, when combined, requires no external powersources to conveniently and safely generate heat, steam and a biocidalchemical agent that destroys contaminating microorganisms or chemicalagents on contaminated objects or surfaces. The present invention doesnot require external sources of power such as electricity or fire.

2. Description of Related Art

Microbial contamination of objects and surfaces such as food contactsurfaces and food service equipment in kitchen environments (e.g.,cutting boards, knives, and utensils), of military clothing, vehicles,and equipment, and of medical, dental, or veterinary instruments canlead to the transmission of infectious pathogens and the spread offood-borne illnesses and other diseases. Inactivating these pathogenicmicroorganisms to prevent infection and the spread of disease requiresdisinfection or sterilization through the application of a lethaltreatment of commensurate stringency.

Military activities in remote or open field locations often experienceconditions wherein electrical power, water, or fire is unavailable, oflimited availability, or undesirable in such environments. Militarysurgical teams in such instances require clean, safe, sterileinstruments and equipment that contact the patient. While pre-packagedinstruments transported to these locations arrive initially sterile,they become contaminated following their use in medical procedures. Itis absolutely necessary that these contaminated instruments be cleanedand sterilized before subsequent use with additional patients to preventthe transmission of infection and disease.

In representative hospitals, clinics, and laboratories, contaminatedinstruments are customarily washed, scrubbed, sealed in germ-freepackaging, and then sterilized in an autoclave for re-use. Typically,pressurized steam autoclaves powered by electrical power generate heatand/or steam as the agents most frequently used to sterilize glass,metal, or high-melting plastic tools and instruments. However, it iscurrently not possible to carry out such sterilization techniques inmilitary facilities located in remote or open field environments wherelarge pressurized steam autoclaves are not available, and whereinelectrical power, water, or fire is unavailable, of limitedavailability, or undesirable. The challenge of replenishing the supplyof available sterile instruments in these circumstances often requirestransporting contaminated equipment via aircraft to distant hospitalswith the facilities to support the operation of a pressurized steamautoclave. In order to safely and effectively sterilize contaminatedsurgical instruments for immediate re-use on site in these remote ordifficult-to-access locations with limited power supplies, it isnecessary to consider alternatives to electrical- or fossil fuel-poweredsterilization using autoclaves.

There are several prior art sterilization methods used to sterilizeobjects such as field feeding equipment, military equipment, or surgicaltools. However, such prior art methods are not suited for remote, fieldenvironments such as those typically found in military situations or incountries ravaged by disease and famine wherein international healthworkers and doctors conduct medical operations in situ. The most widelyused chemical disinfectants are halogens, ozone, chlorine dioxide,chloramines, and ethylene oxide. Among them, the most effectivedisinfectant is chlorine. Ozone and chlorine dioxide are very close tochlorine with respect to effectiveness. Other halogens, such as bromineand iodine, are less effective as is ethylene oxide, although, undercertain circumstances, one of these agents may be recommended over theothers. For example, ethylene oxide is frequently used to fumigatetextiles because ethylene oxide is readily decomposed to non-toxicproducts on contact with air.

The major disadvantages of the two most effective chemicaldisinfectants, i.e. chlorine and ozone, are problems related to theirstorage, transport, and generation. Chlorine is stored as a gas in heavypressurized cylinders. Ozone is unstable, and is generated in situ,which requires a source of electricity. Heavy equipment is typicallyinvolved whether electrical power is obtained from batteries orgenerators. Ozone, moreover, is usually generated in an electrochemicalcell which must be continuously supplied with air at one electrode andwater at the other electrode thereby necessitating the use of furthermechanical and/or electrical implements and devices. Other halogens andtraditional disinfectants, such as hydrogen peroxide, chloramines, andethylene oxide, are unstable, not sufficiently effective, or difficultto handle.

Another technique for sterilizing or disinfecting objects entails theuse of the disinfectant Super Tropical Bleach (sodium hypochlorite inaqueous solution). This bleach is typically used to decontaminatemilitary equipment, vehicles, weapons, clothing, and field-kitchenequipment. However, hypochlorite cannot be generated on-site and must betransported and stored in large, heavy containers. Hypochlorite is alsocaustic and difficult to ship due to its potential health hazards.Furthermore, hypochlorite is especially corrosive to metal surfaces suchas those found on military equipment, vehicles, weapons systems, andgenerators. Additionally, hypochlorite disinfection producesenvironmentally hazardous by-products including carcinogenic compoundsthat endanger human health. The disadvantages of Super Tropical Bleachprevent its use in disinfecting contaminated surgical instruments inremote or far-forward environments.

The use of radiation to achieve disinfection and sterilization also hasmany disadvantages. Whether the radiation takes the form of ultravioletlight, X-rays, or nuclear emissions, it is usually applied in anenclosed environment. The generation of such high-energy radiationeither involves electricity, for ultraviolet light and X-rays, orlead-lined containers and special handling, in the case of shieldedinstallations for radioactive nuclides. Factors such as high power,heavy and complex equipment, and the necessity of extreme safetyprecautions preclude the rapid deployment of radiation sources from onelocation to another, especially in remote areas.

Thus, these aforesaid sterilization and disinfection methods that usechemicals or radiation are not suitable for remote, field operations andin situations wherein electrical power is not available or of limitedavailability.

Another known sterilization and disinfection technique involves chlorinedioxide synthesis. Known chlorine dioxide synthesis techniques typicallyuse one of three methods: (a) electrochemical, (b) acidification, and(c) oxidation. Each of these three methods is described in the ensuingdescription.

a) Electrochemical Methods

The electrochemical methods involve the formation of chlorine dioxidefrom chlorine-containing compounds of lower chlorine oxidation number,such as, but not limited to, chloride, hypochlorite, or chlorite ions,by passage of an electrical current through solutions of theseelectrolytes in an electrochemical cell. For example, Tremblay PatentApplication Publication No. U. S. 2003/0006144 discloses anelectrochemical method that requires the production of relatively largevolumes of electrolyte that must be constantly stirred and transportedin small amounts using an electrochemical cell. The electrochemical celltypically comprises liquid reservoirs, pumps, and batteries which arenot only heavy, voluminous and bulky, but also are difficult to operatewithout a source of electricity or fire. Furthermore, although potabledrinking water can be produced from such an electrochemical cell,Herrington U.S. Pat. No. 6,736,966 do not disclose achievement ofsterilization, the more rigorous state of complete elimination ofmicroorganisms.

b) Acidification

Acidification involves the formation of chlorine dioxide by protontransfer to chlorite ion. The chlorous acid so produceddisproportionates to yield chloride and chlorate ions, and variousamounts of chlorine dioxide. Kampa Patent Application Publication No.U.S. 2004/0062680 (“Kampa”) discloses an apparatus and method whereinthe components needed for reaction are sequestered into two compartmentsseparated by a rupturable membrane. This method can be used foracidification if a component in one compartment is a proton-releasingreagent, and the other component in the second compartment is a chloritesalt. Such a technique is prone to several problems the solutions ofwhich make the techniques disclosed in Kampa undesirable for fieldsterilization. For example, the acidification reactions may be too slowand require expensive catalysts that do not last long as is found inOstgard U.S. Pat. No. 6,399,039. Barenberg et al. U.S. Pat. No.5,980,826 (“Barenberg”) discloses a chemical combination which is avariation on the acidification method and uses a hydrophobic material tocontact a contaminated surface, a hydrophilic material to introducewater needed to release protons, a proton-releasing reagent and achlorite salt. However, the chemical combination described in Barenbergrequires bulky material and precise control in order to achieve thecorrect amount of moisture in the atmosphere. Thus, the techniquedescribed in the aforesaid Barenberg patent is not suited to therigorous sterilization requirements associated with remote fieldoperations as is frequently found in military applications (e.g., highaltitudes or desert climates). Klatte U.S. Pat. No. 6,645,320 describesa technique involving the use of a zeolite to store the proton-releasingcompound and chlorite salt in a mixed, but unreactive state. However,such a technique uses costly materials, requires fluid flowmethodologies, and is not suited to the sterilization requirementsassociated with remote sites wherein electrical power is not available.

c) Oxidation

Oxidation methods require the formation of chlorine dioxide by using achemical oxidant to raise the oxidation number of a chlorine-containingchemical such as sodium chlorite. A widely used oxidant is chlorine gas,which must be transported to the site in a heavy pressurized gascylinder. In addition, there are problems in gas delivery which requireconsiderable heavy, energy-consuming equipment to make the deviceeffective as a biocide. Such a technique is disclosed in Jefferis, IIIet al. U.S. Pat. No. 4,908,188.

Thus, as shown above, none of these aforementioned chlorine dioxidesynthesis methods provide a safe, convenient, reliable means forgenerating sufficient chlorine dioxide to achieve sterilization ofobjects in a relatively short time and in remote locations.

There are also disinfection methods and techniques that do not usechlorine dioxide. Such a method is described in Tarancon U.S. Pat. No.5,229,072. This technique uses a fluorine-containing interhalogencompound such as gaseous chlorine trifluoride which hydrolyzes uponcontact with liquid water or gaseous water vapor to release biocidalproducts. This technique necessitates the safe handling of corrosive andexpensive materials as well as toxic gases. Furthermore, this techniquerequires a chamber of controlled humidity to effectuate disinfection.Thus, this technique is not suited for remote field operations.

There are other prior art techniques and methods that are variations ofthe techniques and methods described in the foregoing description. Forexample, Rosenblatt et al. U.S. Pat. No. 4,504,442 also discloses theuse of chlorine dioxide gas as a chemosterilizing agent. Contaminatedsurfaces are contacted with an effective amount of gaseous chlorinedioxide for a predetermined amount of time to kill bacterial spores at atemperature that does not overly exceed ambient temperature. Rosenblattet al U.S. Pat. No. 4,681,739 discloses the use of chlorine dioxide gasas a chemosterilizing agent. The method comprises the step of exposing asurface contaminated with spores to a humid gaseous environment and thenexposing the spores to an amount of gaseous chlorine dioxide. Drake U.S.Pat. No. 6,042,802 discloses a method and apparatus for generating andusing chlorine dioxide. Specifically, this patent teaches a method forgenerating a volume of disinfectant/sterilant fluid having apredetermined concentration of chlorine dioxide. The method includestransferring the generated chlorine dioxide gas to a separatedisinfectant chamber containing a liquid solvent. The liquid solvent ischosen from the group consisting of water, alcohol, organic solvents andchlorinated solvents.

Aoyagi U.S. Patent Application No. U.S. 2003/0136426 discloses a methodfor cleaning and sterilizing medical devices. The medical devices areimmersed in a chlorine dioxide solution. Thereafter, the medical deviceis placed in a chlorine dioxide gas atmosphere. Nelson et al. PatentApplication Publication No. U.S. 2004/0101438 discloses a method andapparatus for sterilizing or sanitizing a container for food. Chlorinegas is produced either inside or outside the container and thencirculated inside and throughout the container. The chlorine gas is thenremoved from the container and is reclaimed by dissolving it in asolvent. However, the foregoing techniques and methods suffer from oneor more of the drawbacks and disadvantages described in the foregoingdescription (i.e. complex, bulky and expensive equipment, equipment thatrequires electrical power, etc.) and therefore, are not suited for usein remote locations wherein electrical power is not available or oflimited availability, or wherein fire is either not available orundesirable.

Thus, it is apparent that currently, there is no portable, power-freemethod to safely, conveniently, and controllably generate sterilant ordisinfectant in field environments, particularly in remote locations,that can be used to sanitize field feeding equipment, decontaminatemilitary clothing or equipment, or sterilize medical instruments. Withrespect to sterilizing contaminated medical or surgical instruments,there is currently no alternative to the costly and inconvenientpractice of collecting the used medical or surgical instruments andtools, removing them from the remote field environment, transportingthem to a distant site where they are sterilized in electrically-poweredhospital steam autoclaves, packaged, and then transported back to theremote field environment for reuse. What is needed is a technique whoseprecursors can be safely and readily transported to field locations(including difficult-to-access environments or remote locations) andthat requires no external power sources to controllably and safelygenerate a lethal biocidal chemical agent to sterilize objects orsurfaces (e.g. field feeding equipment, medical instruments, militaryclothing or equipment, etc.) on site so that such objects can becleaned, sterilized, and reused quickly and safely.

SUMMARY OF THE INVENTION

The present invention is directed towards portable and power-freesterilization or disinfection of contaminating microorganisms throughthe use of chemical energy in the form of a chemical combination ofsafe, dry reagents that mix in water to produce a biocidal chemicalagent, heat, and humidity. The atmosphere thus created is sufficientlylethal to destroy contaminating microorganisms, biological agents orbio-threats to human health such as viruses, parasites and oocysts,bacteria and spores that cause food-borne illness, infection, ordisease. The chemical combination of the present invention isspecifically configured for use in situations where autoclave facilitiesare unavailable or remote, where electricity or fire are not available,or the use of fire is dangerous or otherwise disadvantageous, or theavailability or accessibility of electrical power and water is limited.

The chemical combination of the present invention concomitantly producesbiocidal chemical agent, heat, and humidity. The present invention isspecifically configured to sanitize, disinfect, decontaminate, orsterilize field feeding equipment, utensils, food service countertops,cutting boards, knives, utensils, food contact surfaces, militaryequipment, vehicles, weapons, and clothing, and surgical instruments,dental instruments, metal or high-melting plastic tools and devices.Tests and experiments have shown that after exposure to the conditionsof heat, humidity, and the biocidal chemical agent acting in concert,the contaminating microorganisms show no detectable formation ofcolonies when recovered on appropriate media. The chemical combinationof the present invention is also configured to take place safely inplastic containers, rubber containers, aluminum or stainless-steelcontainers, and autoclaves to heat, disinfect, or sterilize objects.

In one embodiment, the chemical combination of the present inventioncomprises constituents that can be varied in appropriate quantities orrelative proportions. Specifically, this chemical combination compriseswater or an aqueous solution, a chemical oxidant having the capacity toliberate a biocidal intermediate, a chemical reductant having thecapacity to reduce the chemical oxidant, an effector that interacts withthe chemical oxidant releasing biocide and inducing chemical reactionbetween the chemical oxidant and the chemical reductant, and a metallicreductant that has the capacity to controllably reduce water or anaqueous solution.

In another embodiment, the chemical combination of the present inventiongenerates combinations of heat, humidity or steam, and a biocidalchemical agent that decontaminates, disinfects, or sterilizes objects orsurfaces contaminated with target microorganisms, but does not use ametallic reductant. In such an embodiment, the chemical combination ofthe present invention comprises water or aqueous solution, a chemicaloxidant with the capacity to liberate a biocidal chemical agent throughchemical reaction, a chemical reductant having the capacity to reducesaid chemical oxidant, and an effector that liberates the biocidalchemical agent and induces further chemical reaction between thechemical oxidant and the chemical reductant. Preferably, the chemicaloxidant is sodium chlorite, the chemical reductant is sodium sulfite,and the effector is sodium hydrogen ascorbate. The resulting aqueouschemical reaction is exothermic. Thus, it releases thermal energythereby increasing the temperature and the relative humidity of thesurrounding atmosphere. Upon addition of the water or water solutions,the ascorbate-initiated reduction of chlorite begins with the transferof an electron from chlorite to ascorbate that causes a release of heat,a decrease in the solution pH, and the release of chlorine dioxide inboth heated gaseous and aqueous forms. After initiation by ascorbate,chemical reaction intermediates generated by the ascorbate-chloriteinitial reaction induce chemical reaction between the oxidant chloriteand the reductant sulfite, which produces heat and increase the solutionpH. The resulting heated chlorine dioxide is a lethal biocidal agent aseither a heated gaseous and/or aqueous solution. Carrying out thisaspect of the present invention inside a closed container can maintainan atmosphere of biocidal chemical agent, heat, and humidity for a timesufficient to effect the destruction of all contaminating microorganismspresent.

The heat generated by the chemical reaction of these constituents can besufficient to boil water, thereby bathing the objects to be disinfectedor sterilized in an atmosphere of moist heat containing a biocidalchemical agent. The final products yielded by the chemical combinationof the present invention are environmentally benign dehydroascorbicacid, carbon dioxide, sodium chloride, sodium sulfate, and chlorinedioxide.

In the preferred embodiment, the chemical effector is chosen from thegroup of protonated ascorbate-species consisting of hydrogen ascorbateion, ascorbic acid, and ascorbate dianion. In other embodiments, theeffector can be other chemical compounds, such as reducing sugars, orother organic acids, such as erythorbic acid or tartaric acid and theirrespective ions.

In one embodiment of the chemical combination of the present invention,chlorite is used as the chemical oxidant to generate the biocidalchemical agent chlorine dioxide. In another embodiment, the chemicalcombination of the present invention contains a chemical oxidant thatdoes not contain chlorine. This particular chemical oxidant can be usedin addition to, or in place of chlorite, which is the preferred oxidant.For example, the chemically similar halogen-containing oxidant bromatecould be used. Additional oxidants could include otherhalogen-containing species such as hypobromite or bromite, andhalogen-free species such as persulfate, or hydrogen peroxide. In theseembodiments, the exposure of the chemical oxidant to the effector, suchas ascorbate, produces reactive potential or actual biocidal agents suchas bromine dioxide, sulfate radical ion, or hydroxyl radical,respectively.

In a preferred embodiment, the chemical combination of the presentinvention uses chlorite as the chemical oxidant and sulfite as thechemical reductant. It is possible to construct other embodiments withchlorite, in which the reductant is some other reducing species such as,but not limited to, hypophosphorus acid or phosphorus acid. Theseadditional reductants can be used in further embodiments incorporatingother halogen-based or non-halogen-based oxidants.

In another embodiment, the present invention is directed to a chemicalcombination that generates copious and sustainable amounts of heat,humidity or steam, and a biocidal chemical agent that decontaminates,disinfects, or sterilizes objects or surfaces contaminated with targetmicroorganisms. In this embodiment, the chemical combination compriseswater or water solutions, a chemical oxidant having the capacity toliberate a biocidal intermediate, a chemical reductant having thecapacity to reduce the chemical oxidant, and effector that interactswith the chemical oxidant to release biocide and induce chemicalreaction between the chemical oxidant and the chemical reductant, and ametallic reductant blended with an activator. The combination of themetallic reductant blended with the activator has the capacity tocontrollably reduce water or aqueous solutions. Preferably, in thisembodiment, the chemical oxidant is sodium chlorite, the chemicalreductant is sodium sulfite, the effector is sodium hydrogen ascorbate,and the metallic reductant is magnesium blended with 5 mole percentiron, and referred to hereinafter as Mg(Fe). These aforementionedconstituents are mixed in a single reactor vessel. Preferably, the drycomponents of the chemical combination are first added together.Chemical reactions do not occur until after the addition of water orwater solutions. Upon mixing the dry constituents with water, exothermicmagnesium reduction of water to dihydrogen occurs. At approximately thesame time, chlorine dioxide is released as ascorbate reacts withchlorite.

In an alternate embodiment, the oxidant, e.g. chlorite, is firstdissolved in water, and the remaining dry constituents, the chemicaloxidant, effector and metallic reductant, are then added to the aqueoussolution comprised of water or water solutions and the chlorite chemicaloxidant. This embodiment will reduce the output of dihydrogen as themagnesium will reduce both water and dissolved chlorite. As in themagnesium-free aspect of the invention, further embodiments arepossible, wherein the chemical oxidant, chemical reductant, and effectorare replaced by other compounds such as those listed above in theforegoing description.

When all the aforementioned constituents of the chemical combination ofthe present invention have been associated in a suitable container, thischemical combination generates sustainable heat, humidity or steam, anda biocidal chemical agent that destroys contaminating microorganismscapable of inhabiting feeding equipment, food utensils, and food contactsurfaces, military equipment, vehicles, and clothing; or used surgicalinstruments or medical equipment.

The heat generated by the chemical reaction of these constituents can besufficient to boil water, thereby bathing the objects to be disinfectedor sterilized in an atmosphere of moist heat containing a biocidalchemical agent. The final products yielded by the chemical combinationof the present invention are environmentally benign magnesium hydroxide,dehydroascorbic acid, carbon dioxide, sodium chloride, sodium sulfate,and chlorine dioxide.

In addition to iron, smaller amounts of other transitional elements suchas vanadium, manganese, and cobalt can act as magnesium activators andbe blended (or milled) into the magnesium. In this aspect of theinvention, where a temperature within the disinfection chamber above100° C. is maintained for several minutes, other metallic reductantssuch as calcium or sodium amalgam may be used in additional embodiments.

A significant advantage of the chemical combination of the presentinvention is that it is configured for conditions and situations whereinelectrical power is either not available or is of limited availability.For example, the present invention provides a solution to thelongstanding problem wherein the transportation of power sources, suchas generators, is either difficult or not possible, or wherein the useof fire to generate heat is either not desirable or not possible.

Another important advantage of the present invention is that it solvesthe problems associated with prior art techniques and methods whereinthe transportation of disinfectant chemicals or solutions is difficultdue to the bulkiness or large volume and/or weight of such chemicals,solutions and required equipment.

A further advantage of the present invention is that it eliminates theproblems related to the transportation of hazardous chemicals that posehealth and environmental risks.

Other features and advantages of the present invention will be apparentfrom the following description in which the preferred embodiments havebeen set forth in conjunction with the accompanying figures.

BRIEF DESCRIPTION OF THE DRAWINGS

In describing the preferred embodiments of the invention reference willbe made to the series of figures briefly described below.

FIG. 1 is a graph that shows the temperature profiles of one embodimentof the chemical combination of the present invention and its individualcomponents.

FIG. 2 is a graph that shows a sustainable temperature profile occurringin a 20 L insulated container with a reaction combination comprisingwater, chlorite, sulfite, ascorbate, and magnesium/iron.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is directed toward a chemical combination for usein portable and power-free sanitization, decontamination, disinfection,or sterilization of objects, equipment, or surfaces contaminated withmicroorganisms or chemical compounds capable of transmitting food-borneillnesses, infections, or disease.

In one embodiment, the chemical combination of the present inventionutilizes a metallic reductant comprising magnesium and an ironactivator. In another embodiment, the chemical combination of thepresent invention is magnesium-free. However, in both of theaforementioned embodiments, the chemical combination comprises water orwater solutions, a chemical oxidant, a chemical reductant, and aneffector.

Thus, in one embodiment, the chemical combination of the presentinvention comprises water or water solutions, a chemical oxidant, achemical reductant, an effector and a metallic reductant. The water orwater solutions serve as a solvent for the chemical oxidant, thechemical reductant, and the effector, and as a reactant for the metallicreductant. The water or water solutions also serve as a source of steam.The chemical oxidant has the capacity to liberate a biocidalintermediate. The chemical reductant has the capacity to reduce thechemical oxidant. The effector, in less than a stoichiometric amount,induces an electron transfer reaction between the chemical oxidant andthe chemical reductant. Reaction of the chemical reductant with thechemical oxidant provides a biocidal intermediate and generates heat andsteam. The resulting biocidal intermediate is in the form of adisinfecting solution and gas (or vapor) that can be applied tocontaminated surfaces and objects in order to sanitize, decontaminate,disinfect, or sterilize such surfaces, objects, or equipment. Themetallic reductant has the capacity to sustainably generate heat andsteam. Furthermore, as will be apparent from the ensuing description,when the chemical combination of the present invention is carried out ina closed container, it produces and maintains in said container anenvironment of disinfecting biocide gas and solution and an atmosphereof steam or of high relative humidity and temperature for a period oftime sufficient to destroy all contaminating microorganisms and/orchemicals present.

As explained in the foregoing description, the chemical combination ofthe present invention uses water or water solutions. One example of asuitable water solution is a salt-water solution. The water or watersolution has several functions. Water (or a water solution) stabilizesreducing entities derived from a metallic reductant, such as magnesium,serves as the oxidant of the metallic reductant, and serves as themedium for reactions of dissolved components. Importantly, it serves asa source of steam. For example, when magnesium blended with iron ismixed with an aqueous salt solution, heat is generated in addition toother reactions, and steam evolves.

In accordance with the preferred embodiment of the invention, thechemical oxidant is a halogen-based oxidant. In one embodiment, thehalogen-based oxidant is a chlorine-containing compound that has thecapacity to liberate chlorine dioxide. In the preferred embodiment, thechlorine-containing compound is sodium, lithium, potassium or any othermetal ion salt of chlorite.

In another embodiment, the chemical oxidant is not a chlorine-containingcompound, but instead, is a chemically analogous halogen-containingoxidant such as hypobromite, bromite, or bromate, or it is a chalcogenspecies such as persulfate, or it is hydrogen peroxide. In such anembodiment, exposure of such a chemical oxidant to an appropriateeffector such as ascorbate produces reactive potential or actualbiocidal intermediates such as bromine dioxide, sulfate radical ion, orhydroxyl radical.

In accordance with the invention, the chemical reductant has asufficiently high reduction potential to reduce the aforesaidchlorine-containing compound to chloride ion. Thus, in a preferredembodiment, the chemical reductant is a reducing compound or ion chosenfrom a representative group of such reducing agents, for example, sodiumsulfite, sodium dithionite, hypophosphorus acid, iron(II) chloride(ferrous chloride), and mixtures thereof. However, it is to beunderstood that the chemical reductant can be realized by other suitableand appropriate reducing compounds or ions.

The effector, in less than a stoichiometric amount, induces electrontransfer reaction between the chemical oxidant (e.g. chlorine-containingoxidant) and the chemical reductant and makes this reaction kineticallyfavorable. When the chemical oxidant is a chlorine-containing compound,the effector facilitates reduction of the chemical oxidant to a chlorideion so as to provide a reaction intermediate comprising chlorine dioxideand to generate heat and steam. Specifically, the effector induces thereductant to react with the oxidant by electron transfer therebyaccelerating the oxidation-reduction reaction. It has been found thatusing an ascorbate effector as an inductor of the chlorite-sulfitereaction and combining this reaction with iron-activated magnesiumproduces a sustainable surge of heat with production of biocidalchlorine dioxide. Thus, in accordance with the invention, the effectoris preferably chosen from a representative group consisting of ascorbicacid, erythorbic acid, tartaric acid, or other organic acids, or theirrespective ions, or a reducing sugar. For example, in the preferredembodiment, the effector is sodium hydrogen ascorbate.

Although the prior art recognizes ascorbate as a reactant, the prior artdoes not teach, suggest, or recognize the use of ascorbate as aneffector. For example, Simpson U.S. Pat. No. 6,440,314 (“Simpson”)discloses a technique wherein ascorbic acid is used to remove chloritefrom aqueous solution by an oxidation-reduction reaction which produceschloride ion and dehydroascorbic acid. Specifically, Simpson teaches theuse of ascorbic acid as a common reactant. Teruo et al. European PatentNo. 0196075 (“Teruo”) teaches the use of ascorbic acid to accelerate thedestruction of chlorite in a contact lens cleaning solution. Teruotreats ascorbic acid as any one of a number of acids used to convert thechlorite ion to chlorous acid which then decomposes. However, neither ofthese patents teaches, suggests, or recognizes the use of ascorbate asan effector.

In the preferred embodiment, the metallic reductant is magnesium milledor blended with 5 mole percent iron. In one embodiment, this metallicreductant is configured in a form with high surface area (such aspowders, turnings, ribbons or wires) which may be provided alone ordisbursed in an inert porous matrix and which can further be configuredas a flat pad, sphere, a cylinder, a block or irregularly shaped formwhich permits reaction upon contact with a liquid solvent such as wateror water solutions. Such a form of metallic reductant is described inTaub et al. U.S. Pat. No. 5,517,981, the disclosure of which isincorporated herein by reference.

In the preferred embodiment of the chemical combination of the presentinvention non-zero enthalpic reactions are represented by reactions 1-4.

Mg+2H₂O→Mg(OH)₂+H₂+352.97 kJ/mol   (1)

2Mg+ClO₂ ⁻+4H⁺→2Mg²⁺+Cl⁻+2H₂O+1,504.5 kJ/mol   (2)

ClO₂ ⁻+2SO₃ ²⁻→Cl⁻+2SO₄ ²⁻+648.3 kJ/mol   (3)

5ClO₂ ⁻+2H₂O+2.46 kJ/mol→4ClO₂+Cl⁻+4OH⁻  (4)

In this preferred embodiment, the chemical combination comprises waterand the chemical oxidant is the chlorine-containing compound chlorite,the chemical reductant is sulfite, and the metallic reductant is Mg(Fe).The net combination of reactions 1-4 acts to release heat.

The reaction of Mg(Fe) with a salt-water solution produces heat, steamand by-product dihydrogen gas. The chlorite ion suppresses the volume ofby-product dihydrogen gas that is released by the reducing action of themetallic reductant Mg(Fe). Chemical additives that can suppress thedihydrogen gas produced by the Mg(Fe)-water chemical reaction includecopper(II) chloride, oxyhalogenites, or sodium chlorite ion.

Introduction of sodium hydrogen ascorbate as the effector to thechlorite-sulfite reaction causes acceleration of the chlorite-sulfitereaction such that it becomes a practical source of heat and chlorinedioxide. It has been found that in the absence of an effector thatfavors electron transfer, the reaction between reductant and oxidant,such as that between sulfite and chlorite ions, is relatively slow. Ithas also been found that introducing a sodium hydrogen ascorbateeffector to the chlorite-sulfite reaction accelerates thechlorite-sulfite reaction when the amount of sodium hydrogen ascorbateis less than a stoichiometric amount. As a result, the acceleratedchlorite-sulfite reaction becomes a practical source of heat andchlorine dioxide. Thus, upon transfer of an electron from hydrogenascorbate ion (AH⁻) to chlorite ion (ClO₂ ⁻), very rapid chemicaltransformations occur, and the stable but reactive chemical specieschlorine dioxide (.ClO₂) and chlorine monoxide (.ClO) are formed. Thesespecies are reactive, because they contain an odd number of electrons.Unlike the chlorite ion, chlorine monoxide readily accepts an electronfrom the reductant sulfite.

The rapid reaction between chlorite and sulfite that occurs in thepresence of the ascorbate effector (i.e. hydrogen ascorbate ion) isrepresented by the following sequence of reactions:

.ClO+SO₃ ²⁻→ClO⁻+SO₃.⁻  (5)

ClO₂ ⁻+SO₃.⁻→.ClO+SO₄ ²⁻  (6)

.ClO+ClO₂ ⁻→.ClO₂+ClO⁻  (7)

The prior art clearly does not teach or recognize the novel combinationof an oxidation-reduction reaction in the presence of an effector suchas hydrogen ascorbate ion (AH⁻), ascorbic acid (AH₂), ascorbate dianion(A²⁻) or erythorbic acid or its respective ions, or tartaric acid, otherorganic acids and their respective ions or reducing sugars, especiallywith the purpose of producing a biocidal agent for sanitizing,decontaminating, disinfecting or sterilizing contaminated objects. Theoxidation state of chlorine in chlorine dioxide (4+) is relativelyhigher than that of chlorine in the chlorite ion (3+). However, inaccordance with the present invention, an electron of the effector (e.g.hydrogen ascorbate ion) is transferred to the chlorite resulting in avery short-lived transient species which, as a result of furtherreactions, leads to the production of chlorine dioxide.

The overall reaction between sulfite and chlorite ions is veryexothermic. The enthalpy of reaction between sulfite and chlorite ionsis approximately −648.3 kJ/mol. In accordance with the invention, themagnesium-water reaction is incorporated with theascorbate-sulfite-chlorite reaction. Such a feature allows the presentinvention to be used in various manners. For example, the chemicalcombination of the present invention can be used in an enclosed device(e.g. autoclave), which is a closed container or pouch constructed ofplastics, rubber, aluminum, stainless steel, etc. When the presentinvention is implemented in an autoclave, sterilization of contaminatingmicroorganisms is accomplished by heating the objects at about 121° C.for an amount of time between about eight and twelve minutes. In orderto achieve this temperature with steam, the interior of the autoclave ismaintained at a pressure higher than normal atmospheric pressure.Otherwise, steam will maintain the temperature at which liquid waterboils, 100° C., at ambient pressures of approximately 1.0 atmosphere(10⁵ Pascal). Therefore, the present invention functions as a chemicalheater which simultaneously releases a powerful disinfectant and heat.

Various experiments and tests were conducted using various embodimentsof the invention and are now described in the ensuing description.

Test 1

The novel result of using ascorbate as an effector or activator of achlorite-sulfite reaction and combining this reaction withiron-activated magnesium results in a sustainable surge of heat withproduction of biocidal chlorine dioxide. This result is shown in FIG. 1which shows temperature-time profiles based on the results of anexperiment conducted in an adiabatic reactor having a total volume of100 mL and a reaction volume of 4 mL. The reactant quantities used inthe experiment were as follows: 0.75 M sodium chlorite, 0.7 M disodiumsulfite, 0.3 M sodium hydrogen ascorbate, and 1.5 g Mg(Fe). A four-foldmolar excess of Mg(Fe) over chlorite ion was used. A control experimentwith 1.50 mg Mg(Fe) and water alone demonstrates a temperature-timeprofile with a temperature peak of roughly 122° C. occurring atapproximately 4.3 minutes after the start of the reaction. A second typeof control test consisting of water, chlorite, sulfite, and ascorbate inwater (in the absence of the Mg(Fe) metallic reductant) displays atemperature-time profile with a maximum temperature of roughly 40° C.occurring at approximately 1.3 minutes after the start of the reaction.Combining all of the constituents of the chemical combination inappropriate quantities in the same reaction volume, the presentinvention shows a temperature-time profile featuring a temperaturemaximum of ≈120° C. occurring significantly earlier (time≈1.75 minutes)and displaying a more rapid rate of ascent to the maximum than thepreviously described profiles. Additionally, this reaction compositionfeatures the production of a yellow solution and a yellow gas formingconcomitantly with the evolution of heat. The yellow gas was collected,isolated, and positively identified by mass spectrometric analysis to bechlorine dioxide (.ClO₂).

FIG. 1 shows the heat or temperature profile for (i) theascorbate-sulfite-chlorite composition without Mg(Fe), (ii) the reactionof Mg(Fe) with water and without the ascorbate-sulfite-chloritecomposition, and (iii) the heat or temperature profile when thecombination of Mg(Fe) and the ascorbate-sulfite-chlorite composition arecombined with water.

As shown by the foregoing description, the chemical combination of thepresent invention, when using a chlorine-containing compound as thechemical oxidant, reacts to heat a sample of water to temperatures ashigh as those that are sufficient to destroy contaminatingmicroorganisms. At the same time, it generates quantities of chlorinedioxide as high as those sufficient to destroy contaminatingmicroorganisms, and, in appropriate configurations, sustains thetemperature profile of the water and/or generation of biocidal chlorinedioxide for times sufficient to destroy contaminating microorganisms.Thus, the chemical combination generates quantities of chlorine dioxidewhich, when combined with the heated water, steam and relative humidity,act in concert for sufficient times to destroy contaminatingmicroorganisms. These features and characteristics of the presentinvention are exemplified by Test 2 and FIG. 2.

Test 2

A composition was formed by mixing 3.3 mol Mg(Fe), 0.25 mol ascorbateion, 1.0 mol sulfite ion, and 1.64 mol chlorite ion in 600 mL of water.As shown in FIG. 2, when this composition is mixed in a relativelylarger twenty liter (20 L) insulated container, the highercontainer-volume-to-surface-area ratio and insulation cause a decreasein heat loss thereby maintaining the maximum temperature for arelatively longer period of time. It was found that maintaining themaximum temperature for a relatively longer period of time enhances boththe thermal destruction of contaminating microorganisms and the biocidalefficacy of the resulting chlorine dioxide, since more time is allowedfor the generated steam to permeate the surfaces to be decontaminated.As a result, the temperature of the contaminating microorganism issignificantly increased which facilitates destruction of thecontaminating microorganism, dissolution of chlorine dioxide and contactbetween the chlorine dioxide and the contaminating microorganisms.

Test 3

A test was conducted to demonstrate the potency of biocidal chlorinedioxide for eliminating the pathogen Staphylococcus aureus, whosestrains are known to cause food-borne illnesses or infectious diseases.In this test, S. aureus cells were suspended in Butterfield's phosphatebuffer diluent with a pH of 7.2. The density of each of these robustcollections of S. aureus suspensions was approximately 10⁷colony-forming-units per mL (10⁷ CFU/mL). For the testing protocol,different suspensions of S. aureus cells were exposed to a singleconcentration of chlorine dioxide ranging from 0-44 ppm at 30° C. for3-5 min before diluting and plating on agar. Cell counts were made onsamples recovered on Baird-Parker Agar with EY-Tellurite and incubatedat 35° C. for 48 hours. Table 1 shows the destruction of S. aureuscultures by addition of aqueous chlorine dioxide solutions. In thesetest results, S. aureus survival was detected only at the most dilutechlorine dioxide solutions (0.044 ppm). However, increasing the exposuretimes from a few minutes to 24 hours for the treatment with 0.044 ppmchlorine dioxide solution resulted in 100% inactivation of thepathogens. This observation is consistent with the lethality of chemicalagents for destroying microorganisms being the mathematical product ofthe concentration of the lethal agent (C) and the time (t) of exposure(C×t).

TABLE 1 [ClO₂] CFU/mL (ppm) ×10⁻⁶ Comment 0.0 9.55 Control 44 0.00 0.03.4 Control 4.4 0.00 0.0 9.55 Control 0.44 0 0.0 3.4 Control 0.044 0.1163.4% survivors 0.044 <1.0 × 10⁻⁴ Exposure over night 0.044 0.00 Exposurefor 24 h

Test 4

A series of tests was conducted to demonstrate the effectiveness of thenovel chemical combination presented in this invention in generatingsufficient biocidal chlorine dioxide, heat, and humidity in a closedcontainer to eliminate three different types of microorganisms. The listof microorganisms evaluated in these tests includes vegetative bacterialcells of Listeria monocytogenes and Escherichia coli, and bacterialspores of Bacillus stearothermophilus. In these tests, the chemicalcomposition comprised 186 g sodium chlorite, 126 g disodium sulfite, 50g sodium hydrogen ascorbate, 24 g iron-activated magnesium powder, and600 mL of water. The samples comprised microorganisms suspended inButterfield's phosphate buffer solution in loosely capped test tubes,then placed inside the closed container in which the chemicalconstituents were mixed. The cells were exposed to the biocidal chlorinedioxide, heat, and humidity generated by the chemical combination forapproximately 60 minutes after initiation of the reaction. Table 2 showsthat complete destruction of each type of microorganism was achieved bythis composition.

TABLE 2 Species Initial CFU/mL Final CFU/mL Bacillus stearothermophilusspores 1.00 × 10⁸ 0.00 Escherichia coli 1.20 × 10⁷ 0.00 Listeriamonocytogenes 1.34 × 10⁸ 0.00

A fraction of the composition used in Test 4 can be successfullyemployed proportionately if the container size required a smaller amountof the composition. For example, if a container half the size of theoriginal was required, then only 300 mL of water would be used withone-half the weights of each component than the amounts used to conductTest 4.

As shown by the foregoing description, the chemical combination of thepresent invention has the capacity to produce and sustain steam, heatand a biocidal intermediate (e.g. chlorine dioxide) so as to achieve anatmosphere that ranges between super-heated steam and a relatively highhumidity at sub-boiling temperatures for durations sufficient to effectthe destruction of contaminating microorganisms. Such an atmosphere canbe achieved in an enclosed container (e.g. autoclave, pouch, plastic,rubber, aluminum or stainless steel containers, etc.) and sustained foran effective amount of time to destroy contaminating microorganisms orbiological or chemical agents. Alternatively, the chemical combinationof the present invention can be used without any enclosed container. Insuch a scenario, the heat, steam and biocidal intermediate are generatedthen distributed over and around objects to be sterilized so as toexpose contaminating microorganisms to the steam, heat, and biocidalintermediate.

Thus, the present invention provides a safe, efficient and inexpensivemethod for chemically generating a biocidal intermediate dissolved inheated water and/or steam which can sanitize, decontaminate, disinfect,and/or sterilize contaminated equipment, objects, or contact surfacessuch as field-kitchen equipment, food-preparation surfaces, utensils,mess kits, military equipment and vehicles, weapons, clothing, usedsurgical instruments, and/or medical equipment. An important feature ofthe chemical combination of the present invention is its flexibilitysuch that it can be implemented in various ways. As shown in theforegoing description, the chemical combination of the present inventioncan be carried out in an enclosed device or container (e.g. autoclave,pouch, plastic bag, etc.) and generate sufficient heat, steam, andbiocidal intermediate levels to safely sterilize or disinfectcontaminated objects within the device in the absence of electricalpower or fire. In such circumstances, the chemical combination cangenerate high temperature of the steam for a sustained duration (e.g.10-12 minutes) and biocidal intermediate levels in an atmosphere rangingfrom superheated steam to high relative humidity at sub-boilingtemperature that are sufficient to destroy contaminating microorganisms.On the other hand, when an enclosed device is not being used to containthe chemical combination, the heat, steam and biocidal intermediate,whether in gaseous form or in solution, is generated then distributedon, over and around the objects to be decontaminated so as to permeatethe contaminated surfaces and objects that must be sterilized anddisinfected.

As shown by the foregoing description, the mass (weight) of the chemicalcombination of the present invention is relatively small requiring aminimum of components and peripheral equipment (e.g. mixing container)thereby allowing the chemical combination to be a lightweight, portable,flexible, safe, easy to transport, and well suited for use in remotefield conditions.

The principles, preferred embodiments and modes of operation of thepresent invention have been described in the foregoing specification.The invention which is intended to be protected herein should not,however, be construed as limited to the particular forms disclosed, asthese are to be regarded as illustrative rather than restrictive.Variations and modifications may be made by those skilled in the artwithout departing from the spirit of the invention. Accordingly, theforegoing detailed description should be considered exemplary in natureand not as limiting the scope and spirit of the invention as set forthin the attached claims.

1-36. (canceled)
 37. A chemical combination of constituents, forreacting to generate a biocidal intermediate, for use in thesterilization and disinfection of objects, said constituents comprising;a liquid solvent comprising an aqueous solution, such as water or watersolutions, having the capacity to function as a source of humidity orsteam; a chemical oxidant having the capacity to liberate a biocidalintermediate; a chemical reductant having the capacity to reduce saidchemical oxidant; and an electron transfer effector compound having acapacity to induce electron-transfer reaction chemistry between saidchemical oxidant and said chemical reductant and to cause said chemicaloxidant to liberate the biocidal intermediate, said effector being anionic conjugate base form of an organic acid parent compound, with theproviso that said effector excludes the acid form of the parentcompound, such that the effector does not contribute protons and doesnot allow reaction to proceed through acidification; wherein upon saidcombination of the constituents, the effector initiates a reduction ofthe oxidant by electron-transfer reaction chemistry, said chemistrybeing by a transfer of an electron from the oxidant to the effector forcausing a release of heat, a decrease in solution pH, and a release ofbiocidal intermediate in heated gaseous and aqueous forms, said reactionbetween the effector and the oxidant inducing chemical reaction betweenthe oxidant and reductant for producing heat and increasing solution pHfor generating heated biocidal intermediate, with the proviso that saidcombination excludes an acid that lowers solution pH from near-neutralpH for affecting said objects to expose any contaminating microorganismsto said intermediate and sterilizing said objects.
 38. The chemicalcombination according to claim 37 wherein said effector comprises therespective conjugate base ions of an organic acid chosen from the groupconsisting of ascorbic acid, erythorbic acid, or tartaric acid.
 39. Thechemical combination according to claim 37 wherein said chemical oxidantis chosen from the group consisting of a metal ion salt of a salt ofchlorate, hypobromite, bromite, bromate, persulfate, and hydrogenperoxide.
 40. The chemical combination according to claim 37 wherein thechemical reductant is chosen from the group consisting of sodiumsulfite, sodium dithionite, hypophosphorus acid, phosphorus acid, andiron(II).
 41. The chemical combination according to claim 37 wherein thebiocidal intermediate is a halogen-based biocidal intermediate.
 42. Thechemical combination according to claim 37 wherein the biocidalintermediate comprises chlorine dioxide.
 43. The chemical combinationaccording to claim 37 wherein the biocidal intermediate is ahalogen-free biocidal intermediate.
 44. The chemical combinationaccording to claim 37 wherein the liquid solvent is a water solution;the chemical oxidant is chlorite; the chemical reductant is chosen fromthe group consisting of sodium sulfite, sodium dithionite,hypophosphorus acid, phosphorus acid, and iron(II); and the electrontransfer effector is the respective conjugate base ions of an organicacid chosen from the group consisting of ascorbic acid in amounts thatare not less than stoichiometric amounts of the chemical oxidant and thechemical reductant, erythorbic acid, and tartaric acid.
 45. The chemicalcombination according to claim 37 wherein said combination occurs in anenclosed container for producing and maintaining in the container anenvironment of disinfecting biocide gas and/or solution and anatmosphere of steam or high relative humidity and temperature for aperiod of time sufficient to destroy any contaminating microorganismsand/or chemicals present.
 46. A chemical combination of constituents,for reacting to generate a biocidal intermediate, for use indisinfecting and sterilizing objects, said constituents comprising; aliquid solvent comprising an aqueous solution such as water or watersolutions having the capacity to function as a source of steam; achemical oxidant having the capacity to liberate a biocidalintermediate; a chemical reductant having the capacity to reduce saidchemical oxidant; an electron-transfer effector compound having acapacity to induce electron-transfer reaction chemistry between saidchemical oxidant and said chemical reductant in order to cause saidchemical oxidant to liberate a biocidal intermediate, said effectorbeing an ionic conjugate base form of an organic acid parent compound,with the proviso that said effector excludes the acid form of the parentcompound, such that the effector does not contribute protons forallowing a reaction through acidification; and a metallic reductanthaving the capacity to reduce said liquid solvent; wherein upon saidcombination of the constituents, the effector initiates a reduction ofthe oxidant by a transfer of an electron from the oxidant to theeffector for causing a release of heat, a decrease in solution pH, and arelease of biocidal intermediate in heated gaseous and aqueous forms,said reaction between the effector and the oxidant inducing chemicalreaction between the oxidant and reductant for producing heat andincreasing solution pH for generating heated biocidal intermediate, withthe proviso that said combination excludes an acid for lowering solutionpH from near-neutral pH for affecting said objects to expose anycontaminating microorganisms to said intermediate and sterilizing saidobjects; and wherein said electron-transfer reaction is exothermic andgenerates heat, said heat sufficient for converting said aqueoussolution to steam for further sterilizing said objects.
 47. The chemicalcombination according to claim 46 wherein said metallic reductantcomprises iron-activated magnesium.
 48. The chemical combinationaccording to claim 46 wherein said metallic reductant is chosen from thegroup consisting of V, Cr, Mn, Co, Ni, or any other transitional or morenoble metal than magnesium and mixtures thereof.
 49. The chemicalcombination according to claim 46 wherein said activator of the metallicreductant is chosen from the group consisting of Li, Na, K, Be, Ca, Zn,their corresponding amalgams, and mixtures thereof.
 50. The chemicalcombination according to claim 46 wherein said metallic reductant isconfigured in a form selected from a group consisting of powder,turnings, ribbons, or wires, said form for reacting upon contact withsaid liquid solvent having a high surface area.
 51. The chemicalcombination according to claim 46 wherein said effector comprises therespective conjugate base ions of an organic acid selected form thegroup consisting of the respective ions of ascorbic acid, erythorbicacid, or tartaric acid.
 52. The chemical combination according to claim46 wherein said chemical oxidant is chosen from the group consisting ofa metal ion salt of chlorate, hypobromite, bromite, bromate, persulfate,and hydrogen peroxide.
 53. The chemical combination according to claim46 wherein the chemical reductant is chosen from the group consisting ofsodium sulfite, sodium dithionite, hypophosphorus acid, phosphorus acid,and iron(II).
 54. The chemical combination according to claim 46 whereinthe biocidal intermediate is a halogen-based biocidal intermediate. 55.The chemical combination according to claim 54 wherein the biocidalintermediate comprises chlorine dioxide.
 56. The chemical combinationaccording to claim 46 wherein the biocidal intermediate is ahalogen-free biocidal intermediate.
 57. The chemical combinationaccording to claim 46 wherein the liquid solvent is a water solution;the chemical oxidant is chlorite; the chemical reductant is chosen fromthe group consisting of sodium sulfite, sodium dithionite,hypophosphorus acid, phosphorus acid, and iron(II); the electrontransfer effector is the respective conjugate base ions of an organicacid chosen from the group consisting of ascorbic acid in amounts thatare not less than stoichiometric amounts of the chemical oxidant and thechemical reductant, ascorbic acid not in less than stoichiometricamounts, erythorbic acid, and tartaric acid; and the activated metallicreductant is chosen from the group of metallic reductants consisting ofV, Cr, Mn, Co, Ni, or any other transitional or more noble metal thanmagnesium and mixtures thereof, and the activator of the metallicreductant is chosen from the group consisting of Li, Na, K, Be, Ca, Zn,their corresponding amalgams, and mixtures thereof.
 58. The chemicalcombination according to claim 46 wherein the liquid solvent is a watersolution; the chemical oxidant is chlorite; the chemical reductant ischosen from the group consisting of sodium sulfite, sodium dithionite,hypophosphorus acid, phosphorus acid, and iron(II); the electrontransfer effector is the respective conjugate base ions of an organicacid chosen from the group consisting of ascorbic acid in amounts thatare not less than stoichiometric amounts of the chemical oxidant and thechemical reductant, ascorbic acid not in less than stoichiometricamounts, erythorbic acid, and tartaric acid; and the activated metallicreductant is iron-activated magnesium.
 59. The chemical combinationaccording to claim 46 wherein said combination occurs in an enclosedcontainer for producing and maintaining in the container an environmentof disinfecting biocide gas and/or solution and an atmosphere of steamor high relative humidity and temperature for a period of timesufficient to destroy any contaminating microorganisms and/or chemicalspresent.